EP0291064B1 - Leitfähige Pastenzusammensetzung - Google Patents

Leitfähige Pastenzusammensetzung Download PDF

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Publication number
EP0291064B1
EP0291064B1 EP88107672A EP88107672A EP0291064B1 EP 0291064 B1 EP0291064 B1 EP 0291064B1 EP 88107672 A EP88107672 A EP 88107672A EP 88107672 A EP88107672 A EP 88107672A EP 0291064 B1 EP0291064 B1 EP 0291064B1
Authority
EP
European Patent Office
Prior art keywords
particles
conductive
paste composition
metal
conductive paste
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP88107672A
Other languages
English (en)
French (fr)
Other versions
EP0291064A3 (en
EP0291064A2 (de
Inventor
Yasuo C/O Du Pont Japan Ltd. Yamamoto
Akira C/O Du Pont Japan Ltd. Inaba
Takashi C/O Du Pont Japan Ltd. Kitagaki
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to AT88107672T priority Critical patent/ATE89430T1/de
Publication of EP0291064A2 publication Critical patent/EP0291064A2/de
Publication of EP0291064A3 publication Critical patent/EP0291064A3/en
Application granted granted Critical
Publication of EP0291064B1 publication Critical patent/EP0291064B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys

Definitions

  • the present invention relates to a conductive paste composition for manufacturing a thick conductive film such as a thick film circuit and/or a ceramic capacitor.
  • an internal electrode paste for electronic parts such as a ceramic capacitor
  • a metal paste containing a conductive metal powder is most frequently used.
  • the paste can be prepared by kneading the conductive metal powder, an appropriate binder, and a solvent.
  • the paste is applied to a substrate such as a ceramic green sheet by screen printing, and is laminated and pressed. Thereafter, the resultant structure is fired at a high temperature of 1,000°C to 1,350°C, thereby preparing an internal electrode film.
  • a conductive material for the conductive paste particles of noble metals such as gold, palladium, platium, and the like are used.
  • a high conductivity cannot be obtained, and the thickness of the electrode must be increased to maintain a necessary conductivity. For this reason, it is difficult to realize compact, low-cost electronic parts.
  • GB-A-2 152 060 describes a conductive paste composition consisting of an admixture of:
  • a conductive paste composition consisting of an admixture of: a) conductive metal particles having an average particle size of 0.3 to 1.0 ⁇ m; b) particles uniformly coated with a conductive metal and having an average particle size of less than 1 ⁇ m; and c) an organic medium in which the admixture of particles (a) and (b) is dispersed, whereby the conductive metal coated particles (b) are smaller than the conductive metal particles (a).
  • conductive-metal coated particles are mixed with conductive metal particles so as to solve the conventional problem.
  • the conductive-metal coated particles are particles where particles of metal oxides etc. are used as cores, and the core particles are uniformly coated with a conductive metal.
  • palladium particles having an average particle size of 0.3 to 1.0 ⁇ m are mixed with palladium-coated TiO2 particles having an average particle size of less than 1 ⁇ m, so that a conductive film having a better conductivity than a composition containing only palladium particles can be obtained.
  • a ceramic capacitor internal electrode having good dielectric loss tangent and E.S.R. characteristics can be formed.
  • Metals for conductive metal particles used in the present invention include precious metals such as palladium, silver, platinum, and the like and their alloys such as Pd/Ag, as well as a conductive metal such as copper.
  • a firing treatment (to be described later) is preferably performed in a reducing atmosphere.
  • precious metals are preferable, and palladium is most preferable.
  • the average particle size of the conductive metal particles preferably falls within the range of 0.3 ⁇ m to about 1.0 ⁇ m. If the particle size of the conductive metal particles is larger than 1.0 ⁇ m, film continuity is degraded and hence the resistance is increased. On the other hand, if the particle size is smaller than 0.3 ⁇ m, particles (particularly, Pd particles) are agglomerated and are easily converted to particle agglomerates of 1 ⁇ m or more. After such agglomerations of particles are dispersed as a paste, they can no longer have a particle size of 1 ⁇ m or less. Therefore, the filling properties of particles are unpreferably impaired, and the fluidity of the paste is degraded. The paste having such particle agglomerates has poor hiding power, and an electrode film after firing may be discontinued.
  • Conductive particles used in the present invention preferably have good sphericity and uniformity.
  • the conductive-metal coated particles used in the present invention are particles where particles of metal oxides etc. are used as cores, and the core particles are uniformly coated with a conductive metal.
  • TiO2 particles are preferable as cores.
  • particles of BaTiO3, ceramic prepared such that BaTiO3 and oxides are mixed, fired and then milled, Al2O3, SiO2, and high-melting point glass, and the like can be used.
  • Conductive metals for coating include precious metals such as palladium, silver, platinum, and the like and their alloys such as Pd/Ag, as well as conductive metals such as copper.
  • a coating metal is preferably of the same type of metal as that of the conductive metal particles.
  • the average particle size of the conductive-metal coated particles is below 1 ⁇ m. Basically, the conductive-metal coated particles are smaller than the conductive metal particles. If the conductive-metal coated particles are too larger than the conductive metal particles, sintering between adjacent conductive metal particles is suppressed so as to increase the resistance of a conductive film. The conductive-metal coated particles ideally have the particle size enough to be caught in gaps between adjacent conductive metal particles in the packing state.
  • TiO2 particles having an average particle size of 1 ⁇ m or less and preferably, about 0.02 ⁇ m are used as cores, and palladium is coated thereon to provide particles having an average particle size of less than 1 ⁇ m and preferably, about 0.02 ⁇ m.
  • the conductive-metal coated particles used in the present invention can be prepared by a method described in U.S. Patent No. 4,450,188, Japanese Patent Disclosure (Kokai) Nos. 56-150101, 57-41301, 58-37166, and 58-68918.
  • the average particle size used in the present invention indicates "volume-accumulated 50% particle size (D50)” and can be measured by a "microtrack particle size analyzer” (NIKKISO CO., LTD).” or the like.
  • the total content of oxides is set to fall within the range of 1 to 11% by weight with respect to the total content of the conductive metal particles and conductive-metal coated particles, and preferably within the range of 4 to 8% by weight.
  • the main purpose of the organic medium is to serve as a vehicle for dispersion of the particles or finely-divided solids of the composition in such form that it can readily be applied to a ceramic or other substrate.
  • the organic medium must first of all be one in which the solids are dispersible with an adequate degree of stability.
  • the rheological properties of the organic medium must be such that they lend good application properties to the dispersion.
  • the organic medium is preferably formulated also to give appropriate wettability of the solids and the substrate, good drying rate, dried film strength sufficient to withstand rough handling and good firing properties. Satisfactory appearance of the fired composition is also important.
  • organic medium for most thick film compositions is typically a solution of resin in a solvent and frequently a solvent solution containing both resin and thixotropic agent.
  • the solvent usually boils within the range of 130-350°C.
  • resins such as ethylhydroxyethyl cellulose, wood rosin, mixtures of ethyl cellulose and phenolic resins, polymethacrylates of lower alcohols, and monobutyl ether of ethylene glycol monoacetate can also be used.
  • solvents for thick film applications are terpenes such as alpha- or deta-terpineol or mixtures thereof with other solvents such as kerosene, dibutylphtalate, butyl carbitol, butyl carbitol acetate, hexylene glycol, and high boiling alcohols and alcohol esters.
  • terpenes such as alpha- or deta-terpineol or mixtures thereof with other solvents
  • other solvents such as kerosene, dibutylphtalate, butyl carbitol, butyl carbitol acetate, hexylene glycol, and high boiling alcohols and alcohol esters.
  • solvents such as alpha- or deta-terpineol or mixtures thereof with other solvents such as kerosene, dibutylphtalate, butyl carbitol, butyl carbitol acetate, hexylene glycol, and high boiling alcohols
  • thixotropic agents which are commonly used are hydrogenated castor oil and derivatives thereof and ethyl cellulose. It is, of course, not always necessary to incorporate a thixotropic agent since the solvent/resin properties coupled with the shear thinning inherent in any suspension may alone by suitable in this regard.
  • the ratio of organic medium to solids in the paste dispersions can vary considerably and depends upon the manner in which the dispersion is to be applied and the kind of organic medium used. Normally, to achieve good coverage the dispersions will contain complementary by weight 60-90% solids and 40-10% organic medium.
  • the pastes are conveniently prepared on a three-roll mill.
  • the viscosity of the pastes is typically within the following ranges (table 1) when measured at room temperature on Brookfield viscometers at low, moderate and high shear rates:
  • the amount and type of organic medium (vehicle) utilized is determined mainly by the final desired formulation viscosity and print thickness.
  • the conductive paste composition of the present invention can be prepared in such a manner that conductive metal particles, conductive-metal coated particles, and an organic medium are mixed and dispersed by a three-roll mill. This paste can be applied to an alumina substrate by screen printing and can be fired at a temperature of 1,350°C, thereby obtaining an electrode film.
  • the test for the conductivity of the conductive paste composition is conducted as follows.
  • the printed alumina substrate is fired.
  • a firing temperature is increased from room temperature to 1,350°C within 2 hours, a temperature of 1,350°C is maintained for 1 hour, and thereafter, the temperature is decreased to room temperature within 2 hours.
  • the resistance, the thickness, the width, and the length of the resultant electrode are measured, and a specific resistance is calculated from there measured values.
  • Fig. 1 shows the relationship between the weight percent of TiO2 with respect to the total weight of Pd and TiO2 and its specific resistances in electrode films of samples in examples of the present invention.
  • a paste was prepared from 94 parts by weight of palladium particles, 6 parts by weight of TiO2 powder, 9 parts by weight of ethyl cellulose, and 73 parts by weight of terpineol, was printed on the substrate, and was fired, under the same conditions as samples Nos. 1 to 7.
  • Fig. 1 shows the relationship between the percent by weight of TiO2 with respect to the total weight of Pd and TiO2 and their specific resistances in the electrode films in samples Nos. 1 to 7.
  • the specific resistance of the electrode film exhibits the minimum value with respect to the amount of TiO2 of the palladium-coated TiO2 particles.
  • the electrode film containing about 1 to 11% by weight of TiO2 can have a higher conductivity than that of electrode film of the 100% palladium.

Claims (7)

  1. Leitfähige Pasten-Zusammensetzung, bestehend aus einem Gemisch aus
    (a) leitfähigen Metall-Teilchen mit einer mittleren Teilchengröße von 0,3 bis 1,0 µm,
    (b) gleichmäßig mit einem leitfähigen Metall beschichteten Teilchen mit einer mittleren Teilchengröße von weniger als 1 µm; und
    (c) einem organischen Medium,
    wobei das Gemisch aus den Teilchen (a) und (b) in dem organischen Medium dispergiert ist, wobei die mit dem leitfähigen Metall beschichteten Teilchen (b) kleiner sind als die leitfähigen Metall-Teilchen (a).
  2. Leitfähige Pasten-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Teilchen (b) TiO₂-Teilchen sind, die mit dem leitfähigen Metall gleichmäßig beschichtet sind.
  3. Leitfähige Pasten-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Teilchen (a) und (b) aus demselben leitfähigen Metall sind.
  4. Leitfähige Pasten-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das leitfähige Metall ein Edelmetall ist.
  5. Leitfähige Pasten-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß das Edelmetall Palladium ist.
  6. Leitfähige Pasten-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß der Gesamt-Gehalt des TiO₂ in der Zusammensetzung in den Bereich von 1 bis 11 Gew.-%, bezogen auf den Gesamt-Gehalt der Teilchen (a) und (b), fällt.
  7. Leitfähige Pasten-Zusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß der Gesamt-Gehalt des TiO₂ in der Zusammensetzung in den Bereich von 4 bis 8 Gew.-%, bezogen auf den Gesamt-Gehalt der Teilchen (a) und (b), fällt.
EP88107672A 1987-05-15 1988-05-13 Leitfähige Pastenzusammensetzung Expired - Lifetime EP0291064B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88107672T ATE89430T1 (de) 1987-05-15 1988-05-13 Leitfaehige pastenzusammensetzung.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP62117075A JPS63301274A (ja) 1987-05-15 1987-05-15 導電性ペ−スト組成物
JP117075/87 1987-05-15

Publications (3)

Publication Number Publication Date
EP0291064A2 EP0291064A2 (de) 1988-11-17
EP0291064A3 EP0291064A3 (en) 1988-12-28
EP0291064B1 true EP0291064B1 (de) 1993-05-12

Family

ID=14702787

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88107672A Expired - Lifetime EP0291064B1 (de) 1987-05-15 1988-05-13 Leitfähige Pastenzusammensetzung

Country Status (5)

Country Link
EP (1) EP0291064B1 (de)
JP (1) JPS63301274A (de)
AT (1) ATE89430T1 (de)
DE (1) DE3880884T2 (de)
HK (1) HK99693A (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03110711A (ja) * 1989-09-22 1991-05-10 Fuji Kobunshi Kogyo Kk 異方導電性接着剤組成物
GB9211500D0 (en) * 1992-05-30 1992-07-15 First Class Securities Pastes
JPH07211132A (ja) * 1994-01-10 1995-08-11 Murata Mfg Co Ltd 導電性ペーストおよびこれを用いた積層セラミックコンデンサの製造方法
JP2002270189A (ja) * 2001-03-07 2002-09-20 Matsushita Electric Ind Co Ltd 高分子電解質型燃料電池の製造方法とこれを用いた高分子電解質型燃料電池
JP4541789B2 (ja) * 2003-07-14 2010-09-08 日本特殊陶業株式会社 導体用ペースト並びにそれを用いた積層セラミックコンデンサ及び配線基板
JP4914769B2 (ja) * 2007-05-31 2012-04-11 イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー 固体電解コンデンサ電極用導体ペーストおよび該導体ペーストを使用した固体電解コンデンサの電極の製造方法
JP2011218268A (ja) * 2010-04-07 2011-11-04 Murata Mfg Co Ltd 塗膜形成方法および電子部品

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58163102A (ja) * 1982-03-20 1983-09-27 ティーディーケイ株式会社 磁器コンデンサの内部電極用導電性ペ−スト
JPS58178903A (ja) * 1982-04-13 1983-10-20 ティーディーケイ株式会社 導電性ペ−スト
DE3443789A1 (de) * 1983-12-02 1985-06-27 Osaka Soda Co. Ltd., Osaka Elektrische leitende klebstoffmasse

Also Published As

Publication number Publication date
ATE89430T1 (de) 1993-05-15
HK99693A (en) 1993-09-30
EP0291064A3 (en) 1988-12-28
DE3880884D1 (de) 1993-06-17
DE3880884T2 (de) 1993-08-26
EP0291064A2 (de) 1988-11-17
JPS63301274A (ja) 1988-12-08

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